Process of treating hydrocarbon oils



H. T. MAITLAND. PROCESS 0F TREATING'HYDROCABON OILS. `APPLICATION FILED APR l5, |919.

Patented Aug. 15, 1922.

5y Fed uw HAROLD T. MAITLAND, 0F MARCUS HOOK, PENNSYLVANIA, ASSIGNOR TO SUN COM- PANY, 0F PHILADELPHIA, PENNSYLVANIA, A CORPORATION 0F NEW JERSEY.

' PROCESS ,or TREATING HYDRocARBoN oILs.

Specification of Letters Patent. Patentd Aug'. 15, 1922.

Application led April 15, 1919, Serial No. 290,228.

4Treating Hydrocarbon Oils, of which the following is a full, clear, and exact description, reference being had to the accompanying drawings, which form a part vof this specification.

The object of my inventionis to produce,J

by treating mineral' oils, saponifiable oils or organic compounds which will have certain characteristics of animal oils, vegetable oils and resins and which are adapted for various uses, some of the principal of which are for the manufacture of soaps, hydrogenated compounds, greases, drying oils, cutting oils, nitrated, sulphonated and chlorinated compounds, land addition, substitution or oondensation` products, some of which have antiseptic and medicinal properties.

portions with water and is partially soluble The derivative from mineral oil produced by my process has a peculiar characteristic which no other known derivative from min-v ing, in the main, when saponified, the quali` ties of ordinary soaps made from oil of vegetable or animal origin. The product, in

the preferred forms in which I have made it, has also the following specific characteristics: It is odorless, does not become rancid, and when saponified it is soluble in all proin mineral oil, the degree of its solubility depending upon the character of the oil.

The production from mineral oil of sulfoacids or sulfonic compounds which are saponifiable and whensaponified exhibit some of the characteristics of ordinary soap is known. These sulfonated acids, however, are quite dierent from my novel product both in constitution and in certain essential characteristics. Thus the sulfonated acids contain, as their name implies, a large percentage of sulfur, they are soluble in water, and when saponified they do not undergo the process of hydrolytic decomposition which occurs with ordinary soaps. The sulfur content of my products, on the contrary, is

scarcely more than a trace, and exists chiefly in the form of sulfates, which are there as impurities, My product, therefore, is not a sulfo-acid'or a sulfonic compound in any sense, as it is insoluble in'Wa-ter, and it behaves, when saponiiied, like ordinary soap .in that it undergoes the same character of hydrolytic decomposition and exhibits most other, and probably all other, importantv qualities which characterize ordinary soaps.

My new product cannot, by reason of its novelty, be too specifically designated. It is, however, undoubtedly a saponiiable oil or a series of oils and it is scarcely questionable that it is an organic acid of the resin grou The main advantage of my new product is its cheapness, by reason of the cheapness of mineral oils as compared with animal and vegetable oils. It has, however, not only the economical advantage o-f being a derivative from mineral oils, but it has the further economical advantage of being a derivative from materials which are -by-products in the manufacture of lubrieating oils and other standard refined products from crude oils, which by-pinodluct-sA have hitherto either been wasted or only partially utilizedy for the manufacture of products which command a comparatively small price. My product has a muchgreater commercialvalue than lubricating oil itself, making it profitable to so conduct the Whole refining process as to make the production of my newproduct the chief ob- Aj ect.

In an application filed April 15, 1919, Serial No. 290,227, I have set forth two processes having certain novel features in common, which I have therein claimed. I have also claimed therein, specifically, one of the two processes. The present application is confined to the disclosure of the other process, which is herein specifically claimed. v

In vthe accompanying drawing, the figure is a vertical section of a mechanical masticator and digester which I prefer to use in carrying out my process.

It will be understood, however, that the use of any particular apparatus is not essential to the execution of the process; and while the apparatus herein described and illustrated, as well as the precise details of treatment herein set forth, have been demonstrated to be 4 eilicient by practical commercial use, it is not intended to limit or-restrict the invention; within a narrower scope than the claims define.

While any crude petroleum is possibly o r probably adapted for use in the execution of 'my processes', I prefer to use Texas crude oil, or a crude petroleum of that nature on account of the particular group of hydrocarbons and their mobility to conversion which are found in an oil of this kind. The yield of saponiableoils is probably increased by the particular distilling process which I preferably employ to secure the so-called lubricating oil stock from which both lubricating oil and my new product are made, and I shall therefore briefly describe such distilling process; although it -will be understood that the essential steps of my process may be practiced starting vwith any lubricatingl oil stock or distillate,

or at least any lubricating oil stock or distillate made by distilling crude petroleum of the proper grade in the ordinary way. 1 first take the crude petroleum and subject it to a preliminary distillation in which all of the crude 'product is distilled offexcept a relatively small percentage of residuum. The distillates are then subjected to a second distillation, the heavier product remaining in the still being the stock from which lubricating oil may be made. The second distillate is then redistilled, light oils being distilled off, the part remaining also being adapted foruse as lubricating stock. While some saponiiable compounds may be separated from the mineral oil by treatment with fullers earth or bone char, followed by extraction of the saponifiable compounds from the above mentioned materials with some solvent such as alcohol,y ether, benzol, carbon bisulide, etc., I prefer to treat them successively with an acid and an alkali, either first treating with an acid and then with an alkali, or the reverse. ,A certain group of these saponifiable oils may be removed by first precipitating them with an alkali and removing them before treating with sulfuric acid ;l or I may proceed in the usual way, namely: by first treating` the lubrlcatlng stock with an acid, preferably sulfuric acid, with agitation, followed by settlement. AIf sulfuric acid be used, it should not be the anhydride, or even fuming acid, as otherwise sulfo-acids will beformed,

which may be difficult or impossible to eliminate, vor which may make impossible the productlon of the water-insoluble organic acidsought. As a specific example, 2300 barrels of lubricating stock are thoroughly agitatedwith approximately 75 barrels of concentrated sulfuric acid (93.5% H2SO4) and settlement, under appropriate tempera- Masses The middle layer B is composed of approximately 180 barrels of a mixture of sludge and sulfuric acid, the content of the latter being about. 30 per cent.

The lower layer C consists of a small amount of sulfuric acid wit-l1 some sludge in solution.

The lower layer Cshould be drawn off and concentrated.

Then the layer B (or layers B and C if the latter is not separately dra-wn off), to the treatment of which, my process is directed, is subjected to the concurrent action of water and mechanical mastication. The water should be maintained below the boiling point, although it may, if desired, exceed the boiling point toward the end of t-he operation. The water is preferably continuouslyI introduced during the operation of mastication and steam is introduced with the water to maintain the water at the desired temperature.

The special mechanical masticator and digester which I prefer to employ is equipped with asteam jacket a built to withstand a pressure of one hundred pounds to the square inch. The inside o f the digester'as Well as the movable parts contained within it are covered with some acid resisting metal or composition: Special masticating and stirring paddles with a certain sweep or pitch are arranged to revolve with alifting and opposing effect, while stationary interfering bars c serve the double purpose of masticating the sludge and supporting the shafts d and e. The undermost paddle j is hollow and operated by the hollow verti* cal shaft d which moves in an opposite direction to the hollow shaft e containing it.' The edges of this paddle which, in rotation, are at the rear, are provided with small openings g, through which water, .air or steam, or a mixture of two or all of these, may be introduced into the bottom of the digester by means of t-he hollow shaft (l. The bottom of the digester is so constructed that large quantities of water, air or steam, or a mixture of them, may be "introduced by means of an auxiliary pipe or pipes L. The

annular space between' the two shafts is fore the sludge is introduced, the digester is partially filled with cold water at a temperature of approximately degrees C. The desired temperature is maintained throughout the operation by means of the steam jacket and live steam blown into the contents through pipes d .and h. The introduction of the washing liquid may beintermittent, but is preferably continuous, the surplus liquid passing upward through the sludge and out through an overiow c, carrying with it the undesirable mineral acid and certain other compounds which may be subsequently treated but the treatment of which forms no part of the present invention.

The driving mechanism is. so adjusted that the velocity of t-he masticators or paddles may be diminished or increased at will. The' temperature of the contents and the velocity of the masticators are governed entirely by the condition ofthe sludge as the operation proceeds. The sludge is tested vfor mineral acidity at certain intervals and when the mineral acid content has been reduced to such an extent (say to approximately two per cent) as to glve no trouble in the manufactureof the products desired from the sludge, the washing is stopped and the excess washing liquid is syphoned or drawn ofi". During the first part of the operation it is important. that no air be permitted to be mixed with the sludge, as the buoyant air with the sulfur dioxide causes t-he small particles of sludge to rise to the surface and to be vcarried away with the washing liquid. The residual compounds settling to the bottom of digester are saponiiable oils containing some dissolved or suspended mineral oil.

The product of this process is a waterinsoluble organic acid, is practically odorless, does not become rancid, and may be readily 'saponified with caustic alkali or other suitable alkali. The saponiiied prod- Vuct is soluble in all proportions with water,

displays the principal qualities of ordinary soap, and is partially soluble in mineral oil, the degree of its solubility depending upon the character of the oil. The soap forms withA water a colloidal solution similar to that formed with water by any soap of animal or vegetable origin. Such solution, upon drying, partially hydrolyzes-and does not readily dissolve in water the second time; making an ideal road oil or dust preventative. The soap, when mixed with mineral oil and water, forms a homogenous emulsion. The sulfur content of the product is about 0.4 per cent. This practically negligible proportion of sulfur probably ,exists as sulfuric acid or sulfat'es Whose absolutely complete removal has not been effected.

I do not herein claim the product produced bymy process, as' th'same is claimed Having now fully described .my invention, what Iclaim and desire to protect by Letters Patent is: x

l. The process of making a water-insoluble saponiiable oil from the sludge produced inthe treatment with mineral acid of mineral oil stock, which comprises subjecting the sludge to mechanical mastication and concurrently therewith causing water to impenetrate and wash the sludge and dissolve contained mineral acid, the water being heated to such a temperature as to render the sludge of the proper consistency for working, and during the process of washing and mastication supplying fresh water and carrying` off the water that has been used for washing, and continuing the process until the mineral acid content is sufficiently reduced to leave the waterinsoluble sapom'fiable oil speciiied.`

' 2. The process of making a water-insoluble saponifiable oil from the sludge produced i-n the treatment with mineral acid of mineral oil stock, which comprises subjecting a body of sludge to mechanical mastication and concurrently. therewith causing a body of hot water maintained below the boiling point to flow substantially continuously into and upwardly through the body of sludge and outflow at the top,theref by impenetrating and washing the sludge with a volume of water greatly in excess of the volume of water that at any given time is acting upon the sludge, the process continuing until the mineral acid content is reduced to the point required to leave the Water-insoluble saponifiable oil specified.

3. In the manufacture of a water-insoluble saponifiable product from mineral oil, the processv which comprises distilling from the petroleum a relatively heavy distillate adapted for lubricating oil Stock, treating the same with sulfuric acid and separating out the acid sludge, subjecting the sludge to mechanical mastication and concurrently therewith causing water to impenetrate and wash the sludge and dissolve contained mineral acid, the water being heated to such a temperature as to render th'e sludge of the proper consistency for work- A ing, and during the process of washing and mastication supplying fresh water and carrying off the water that has been used for washing, and continuing the process until the mineral acid content is sufficiently reduced to leave the water-insoluble saponifiable product specified.

4. In the manufacture of soap from mineral oil, the process which, comprises dis-4 tilling from the petroleum a relatively heavy distillate adapted for lubricating oil stock, treating the same with sulfuric acid and separating out the acidl sludge, sub- -jecting the sludge to mechanical mastication and concurrently therewith causing Water to impenetra'te and Wash the sludge and dissolve contained mineral acid, the Water being heated to such a temperature as to render the. sludge of the proper consistency for working, and during the process of Washing and mastication vsupplying fresh Water and carrying oil the Water that mames@ has `loeen used for washing, continuing the process until "the mineral acid content is suiciently reduced to leave a Water-insolw hereunto set my hand, at Philadelphia, Pa.,

on this 28th vda of March, 1919.

H ROLD T. MAITLAND.. 

